The present invention relates to a process for producing a fluorine-containing compound such as an industrially useful acid fluoride compound. Further, the present invention provides a novel compound which is useful as a precursor for a fluorine resin material.
Heretofore, as a method for fluorinating all of Cxe2x80x94H portions in a Cxe2x80x94H containing compound to Cxe2x80x94F, a method of employing cobalt trifluoride, a method of direct fluorination with fluorine gas, or a method of carrying out a fluorination reaction in an electrolytic cell using electrolyzed hydrogen fluoride as a fluorine source (hereinafter referred to as electrochemical fluorination) has been known. The method of employing cobalt trifluoride is one wherein the reaction is carried out at a high temperature by a gas-solid reaction, whereby isomerization or bond breakage takes place, and there is a problem that various types of by-products will form. In the case where a direct fluorination method is carried out with fluorine gas, a gas phase method or a liquid phase method has been known. However, the gas phase reaction has a problem that during the fluorination reaction, dissociation of Cxe2x80x94C single bonds takes place, and various types of by-products will form. In recent years, a liquid phase method has been reported.
On the other hand, a method for fluorination in a liquid phase by reacting fluorine gas to a non-fluorine containing compound, has also been reported (U.S. Pat. No. 5,093,432). Further, a method for obtaining an acid fluoride compound by thermal decomposition of a perfluorinated ester compound having a carbon number of at least 16, has also been known, and it is disclosed that the compound can be obtained by direct fluorination of a hydrocarbon ester compound having a corresponding structure in a liquid phase with fluorine gas (J. Am. Chem. Soc., 120,7117(1998)).
The method of employing cobalt trifluoride or electrochemical fluorination has had a problem such that an isomerization reaction takes place or a problem such that breakage of the main chain, a re-union reaction, etc., may occur, and has had a drawback that the desired compound can not be obtained in good purity. In a case where a fluorination reaction is carried out in a liquid phase with fluorine gas, it is common to employ a solvent capable of dissolving fluorine gas, as the solvent for the reaction. However, a hydrocarbon compound as a starting material in a conventional method, usually has a low solubility in a solvent to be used for the fluorination reaction, and accordingly, the reaction is carried out in a very low concentration, whereby there has been a problem that the production efficiency is poor or a problem that the reaction will have to be carried out in a suspension which is disadvantageous to the reaction. Further, if it is attempted to fluorinate a hydrocarbon compound of a low molecular weight in a liquid phase, a problem has been observed such that the reaction yield tends to be remarkably low.
On the other hand, a fluorine-containing monomer such as a perfluoro(alkylvinyl ether) is useful as a starting material monomer for a fluorinated resin having heat resistance and chemical resistance. Heretofore, the perfluoro(alkylvinyl ether) has been industrially produced by a dimerization reaction of a perfluorinated epoxide or by reacting a perfluoroalkanoyl fluoride with a perfluorinated epoxide in the presence of an alkali Or metal fluoride to form a perfluoro(2-alkoxyalkanoyl)fluoride, followed by thermal decomposition. However, such a method has had a problem that control of the reaction of the dimerization reaction is difficult, and the price of the starting material is high and economically disadvantageous.
In the present invention, as a result of various studies on the cause for problems of the conventional methods, firstly, it has been found that the cause for the low yield in the fluorination reaction in a liquid phase with fluorine gas, is attributable to the fact that if the boiling point of the starting material is low, the starting material will react in a gas phase so that a decomposition reaction takes place. Then, it has been found that the decomposition reaction can be prevented by using an inexpensively available Cxe2x80x94H containing compound as the starting material, converting it to a compound of a specific structure which has a high molecular weight so that a gas phase reaction hardly takes place and which is soluble in a solvent for the fluorination reaction, followed by fluorination in a liquid phase. Further, it has been found that the desired fluorine-containing compound can be produced by dissociation of a bonded group after fluorination (for example, dissociation by means of a thermal decomposition reaction or a decomposition reaction carried out in the presence of a nucleophile or an electrophile). Further, an industrial continuous process by recycling the formed compound, has been found.
Namely, the present invention provides a process for producing a fluorine-containing compound, characterized by reacting the following compound (I) with the following compound (II) to form the following compound (III), fluorinating the compound (III) in a liquid phase to form the following compound (IV) and then converting the compound (IV) to the following compound (V) and/or the following compound (VI):
RAxe2x80x94E1 (I)
xe2x80x83RBxe2x80x94E2 (II)
RAxe2x80x94Exe2x80x94RB (III)
RAFxe2x80x94EFRBF (IV)
RAFxe2x80x94EF1 (V)
RBFxe2x80x94EF2 (VI)
wherein
RA, RB: each independently is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group, or a monovalent organic group (RH) which can be converted to RHF by a liquid-phase fluorination reaction,
RHF: a group having at least one hydrogen atom in a group selected from a monovalent saturated hydrocarbon group, a partially halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, and a partially halogeno(hetero atom-containing monovalent hydrocarbon) group, substituted by a fluorine atom;
RAF, RBF: RAF is a group corresponding to RA, and RBF is a group corresponding to RB; and in a case where each of RA and RB is a monovalent saturated hydrocarbon group, a halogeno momovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, or a halogeno(hetero atom-containing saturated hydrocarbon) group, RAF and RBF are the same groups as RA and RB, respectively, or groups having at least one fluorine atom present in the groups of RA and RB substituted by a fluorine atom, and in a case where RA and RB are monovalent organic groups (RH), RAF and RBF are RHF, respectively;
E1, E2: reactive groups which are mutually reactive to form a bivalent connecting group (E);
E: a bivalent connecting group formed by the reaction of E1 and E2; 
EF: the same group as E, or a group having E fluorinated, provided that at least one of RAF, RBF and EF, is not the same group as the corresponding RA, RB and E, respectively;
EF1, EF2: each independently is a group formed by dissociation of EF.
Further, the present invention provides the following novel compounds, provided that in this specification, Cy is a cyclohexyl group, Ph is a phenyl group, and CyF is a perfluoro(cyclohexyl) group;
CF3(CF3CF2CF2O)CFCOOCH2CH (OCH2CH2CH3)CH3,
CF3CF2COOCH2CH2CHClCH2Cl,
CF2ClCFClCF2COOCH2CH2CHClCH2Cl,
CF2ClCF2CFClCOOCH2CH2CHClCH2Cl,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2CH2CHClCH2Cl) CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH (OCH2Cy) CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2Ph)CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(O(CH2)9CH3)CH3,
CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2Ph,
xe2x80x83CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2CHxe2x95x90CH2,
xe2x80x83CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CF3)CF3,
CF3CF2COOCF2CF2CF3,
CF3CF2COOCF2CF2CFClCF2Cl,
CF2ClCFCF2CFClCOOCF2CF2CFClCF2Cl,
CF2ClCF2CFClCOOCF2CF2CFClCF2Cl,
CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CFClCF2Cl)CF3,
CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CyF)CF3,
CF3(CF3CF2CF2O)CFCOOCF2CF(O(CF2)9CF3)CF3,
CF3(CF3CF2CF2O)CFCOO(CF2)3OCF2CyF,
CF3(CF3CF2CF2O)CFCOO(CF2)3OCF2CF2CF3, xe2x80x83FCOCF(O(CF2)9CF3)CF3
FCO(CF2)2OCF2CYF.
Description of Groups Disclosed in the Specification
In the present specification, a monovalent organic group means a monovalent group which essentially comprises carbon atoms. The monovalent organic group may or may not contain fluorine atoms or hydrogen atoms. The carbon number of the monovalent organic group is preferably from 1 to 20, particularly preferably from 1 to 10, from the viewpoint of the solubility in a liquid phase at the time of the fluorination reaction.
In the present specification, the monovalent hydrocarbon group may be a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group, and a monovalent aliphatic hydrocarbon group is preferred. The structure of the monovalent aliphatic hydrocarbon group may, for example, be a straight chain structure, a branched structure, a cyclic structure or a structure having a partially cyclic structure. In the monovalent aliphatic hydrocarbon group, a single bond, a double bond or a triple bond may be present as a carbon-carbon bond. When the monovalent aliphatic hydrocarbon group is a monovalent saturated aliphatic hydrocarbon group, an alkyl group, a cycloalkyl group or a monovalent saturated aliphatic hydrocarbon group having a cyclic moiety (such as a cycloalkyl group, a cycloalkylene group or a bicycloalkyl group, a group having an aliphatic spiro structure, or a group having such a group as a partial structure) may, for example, be mentioned, and an alkyl group is preferred. As the monovalent aromatic hydrocarbon group, a phenyl group, an aryl group or such a group having a substituent, is preferred.
As the halogen atom in the present specification, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom may be mentioned, and a fluorine atom, a chlorine atom or a bromine atom is preferred.
Further, in the present specification, xe2x80x9chalogenoxe2x80x9d means that at least one hydrogen atom present in a group is substituted by at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the group of a halogeno group, a hydrogen atom may or may not be present.
The xe2x80x9cpartially halogenoxe2x80x9d means that a hydrogen atom which is not substituted by a halogen atom is present in the group of a halogeno group. The xe2x80x9cperhalogenoxe2x80x9d means that no hydrogen atom is present in the group of a halogeno group.
In this specification, the halogeno monovalent hydrocarbon group may be a group having at least one hydrogen atom in the above-mentioned monovalent hydrocarbon group substituted by a halogen atom. As such a halogeno monovalent hydrocarbon group, a halogeno alkyl group is preferred. As the halogen atom in the halogeno alkyl group, a fluorine atom, a chlorine atom or a bromine atom is preferred. Further, as a partially halogeno monovalent hydrocarbon group, a partially halogeno alkyl group is preferred. As the perhalogeno monovalent hydrocarbon group, a perhalogeno alkyl group is preferred. The halogen atoms in a perhalogeno alkyl group are preferably composed of fluorine atoms only or fluorine atoms and halogen atoms other than fluorine atoms. As specific examples of these groups, groups disclosed in the following examples of compounds may be mentioned.
In the present specification, the hetero atom-containing monovalent saturated hydrocarbon group may be a group containing in the above-mentioned monovalent saturated hydrocarbon a hetero atom which undergoes no change by the fluorination reaction or a hetero atom group which undergoes no change by the fluorination reaction. Particularly preferred is a group containing in a monovalent saturated hydrocarbon group a bivalent hetero atom or a bivalent hetero atom group which undergoes no change by the fluorination reaction.
The bivalent hetero atom which undergoes no change by the fluorination reaction is preferably an etheric oxygen atom, and the bivalent hetero atom group which undergoes no change by the fluorination reaction may, for example, be xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94SO2xe2x80x94.
As the hetero atom-containing monovalent saturated hydrocarbon group, an alkyl group containing an etheric oxygen atom, or a monovalent aliphatic hydrocarbon group having a cyclic portion having an etheric oxygen atom inserted between carbon-carbon atoms, is preferred. Particularly preferred is an alkoxyalkyl group.
Further, the halogeno(hetero atom-containing monovalent saturated hydrocarbon) group may be a group having at least one hydrogen atom in the above-mentioned hetero atom-containing monovalent saturated hydrocarbon group substituted by a halogen atom, and a halogeno(alkoxyalkyl) group is preferred.
In the compound (I), RA is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group or a monovalent organic group (RH) which can be converted to RHF by a liquid-phase fluorination reaction.
And, RHF is a group having at least one hydrogen atom in a group selected from a monovalent saturated hydrocarbon group, a partially halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group and a partially halogeno(hetero atom-containing monovalent hydrocarbon) group, substituted by a fluorine atom.
When RA is a monovalent organic group (RH), a specific example of such a group is a group (RH1) having a fluorine atom in the desired RHF substituted by a monovalent hetero atom group which can be converted to a fluorine atom by a fluorination reaction, or a group (RH2) having at least one carbon-carbon single bond in the desired RHF substituted by a carbon-carbon double bond or a carbon-carbon triple bond. Further, it is preferred that a hydrogen atom or a fluorine atom is bonded to the carbon atom which forms the carbon-carbon double bond or the carbon-carbon triple bond in RH2.
Here, the monovalent hetero atom group which can be converted to a fluorine atom by a fluorination reaction may be a carboxyl group. Further, the group (RH2) may, for example, be a cyclohexenyl group, a phenyl group, an alkenyl group or an alkynyl group. By a fluorination reaction in a liquid phase, such RH2 becomes a carbon-carbon single bond by an addition of fluorine atoms to the carbon atoms forming an unsaturated bond. For example, by the fluorination reaction, the phenyl group becomes a perfluorocyclohexyl group.
Explanation About Compound (I)
In the compound (I), E1 is a reactive group which is capable of forming a bivalent connecting group (E) by a reaction with E2. Such a bivalent connecting group (E) may be a group which changes or does not change by such a reaction.
As the bivalent connecting group (E), an ester bond-containing group such as xe2x80x94CH2OCOxe2x80x94 or xe2x80x94CH2OSO2xe2x80x94 (provided that the orientation of these groups is not limited). Particularly preferred is xe2x80x94CH2OCOxe2x80x94 from the viewpoint of usefulness of the resulting compound. With respect to E1 and E2 in a case where E is an ester bond-containing group, one of them may be xe2x80x94CH2OH, and the other may be xe2x80x94COX (where X is a halogen atom) or xe2x80x94SO2X. Now, a detailed description will be made with reference to a case where the bivalent connecting group (E) is xe2x80x94CH2OCOxe2x80x94.
In the present invention, it is possible to employ various compounds differing in the structure of RA, as the compound (I). Namely, by carrying out the reaction of the present invention by using a compound (I) having a group (RA) corresponding to RAF in the desired compound (V), it is possible to produce a compound (V) which used to be difficult to obtain by a conventional method. Likewise, various compounds differing in the structure of RB can be employed as the compound (II). As an example of the compound (V) which used to be difficult to obtain by a conventional method, a compound wherein the structure of RAF is complex, or a fluorinated product of a low molecular weight whereby various types of by-products tend to form by the fluorination reaction, may be mentioned. As an example of the latter, a fluorinated product of one wherein the molecular weight of the compound (I) is less than 200, preferably one wherein the molecular weight is from 50 to 200, may be mentioned.
The compound (I) is preferably a compound (Ia) wherein E1 is xe2x80x94CH2OH, particularly preferably a compound (Ia-1) wherein RA is RAH, especially preferably a compound (Ia-2) wherein RA is R1:
RACH2OH (Ia)
RAHCH2OH (Ia-1)
R1CH2OH (Ia-2)
Here, RA has the same meaning as the meaning in the compound (I). RAH is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group or a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group. R1 is an alkyl group, an alkoxyalkyl group, a halogenoalkyl group or a halogeno(alkoxyalkyl) group.
When R1 is an alkyl group, it is preferably a C1-20 alkyl group, particularly preferably a C1-10 alkyl group. The alkyl group may be of a straight chain structure, a branched structure, a cyclic structure or a partially cyclic structure. The alkyl group of a straight chain structure may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl group of a branched structure may, for example, be an isopropyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.
When R1 is an alkoxyalkyl group, it is preferably a group having at least one hydrogen atom present in the above-mentioned alkyl group substituted by an alkoxy group. The carbon number of such an alkoxy group is preferably from 1 to 8. Such an alkoxyalkyl group may, for example, be an ethoxymethyl group, a 1-propoxyethyl group or a 2-propoxyethyl group.
When R1 is a halogenoalkyl group, halogen atoms may be of one type or two or more types, and chlorine atoms, bromine atoms, or chorine atoms and bromine atoms, are preferred. As a specific example of such a group, a chloromethyl group, a bromomethyl group, a 2,3-dichloropropyl group or a 3,4-dichlorobutyl group may be mentioned.
When R1 is a halogeno(alkoxyalkyl) group, halogen atoms may be of one type or two or more types, and chlorine atoms, bromine atoms, or chlorine atoms and bromine atoms, are preferred. As a specific example of such a group, a 1-(3,4-dichlorobutoxy)ethyl group or a 1-(2-bromoethoxy)ethyl group may be mentioned.
Further, the compound (Ia-2) is preferably one wherein R1 is R4(R5O)CHxe2x80x94 (wherein each of R4 and R5 which are independent of each other, is an alkyl group or a halogenoalkyl group), a 2,3-dichloropropyl group or an ethyl group, from the viewpoint of usefulness of the product. Namely, the compound (Ia-2) is preferably a compound (Ia-3), 3,4-dichloro-1-butanol or 1-propanol.
R4(R5O)CHCH2OH (Ia-3)
The compound (Ia-3) is preferably 2-propoxy-1-propanol [(CH3)(CH3CH2CH2O)CHCH2OH] where R4 is a methyl group, and R5 is a n-propyl group.
The following compounds may be mentioned as specific examples of the compound (I). In the following, Cy is a cyclohexyl group, and Ph is a phenyl group.
CH3(CH3CH2CH2O)CHCH2OH,
CH3(CH2ClCHClCH2CH2O)CHCH2OH,
CH3(BrCH2CH2O)CHCH2OH,
CH3[CH2ClCHClCH2CH(CH3)O]CHCH2OH,
CH3CH2CH2OH,
CH2xe2x95x90CHCH2OH,
CH2ClCHClCH2CH2OH,
CH2ClCH2OH,
CH2BrCH2OH,
CyCH2OCH(CH3)CH2OH,
PhCH2OCH(CH3)CH2OH,
CH3(CH2)9OCH(CH3)CH2OH,
PhCH2O(CH2)2CH2OH,
CH2xe2x95x90CHCH2O(CH2)2CH2OH,
CH3CH2CH2OCH2CH(CH3)OH,
CF2ClCFClCH2CH2OH, 
The compound (Ia) is a compound which is readily available or which can readily be synthesized by a known method. For example, 3,4-dichloro-1-butanol can easily be synthesized by a known method disclosed in e.g. U.S. Pat. No. 4,261,901. Further, 2-alkoxyalcohols can be easily synthesized by known methods disclosed, for example, in J. Am. Chem. Soc., 49, 1080(1927), Bull. Soc. Chim. Fr., 1813(1960), Can. J. Chem., 43, 1030(1965), Synthesis, 280(1981). 3-Alkoxyalcohols can easily be synthesized by known methods disclosed, for example, in Tetrahedron Lett., 36,9161(1995), J. Org. Chem., 62, 7439(1997). Alcohols having a dioxolane skeleton can easily be synthesized by known methods disclosed, for example, in Bull. Chem. Soc. Jpn., 70, 2561(1997).
Explanation About the Compound (II)
The compound (I) is reacted with the compound (II). In the compound (II), RB is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group, or a monovalent organic group (RH) which can be converted to RHF by a fluorination reaction in a liquid phase, and embodiments of these groups are the same as RA. With respect to RB, its structure is preferably adjusted in relation with the structure of RA, so that the resulting compound (III) will be readily soluble in a liquid phase to be used at the time of fluorination.
Further, in the present invention, it is preferred that one or each of RA and RB is a monovalent organic group containing fluorine atoms. Further, the fluorine content in the compound (III) (the proportion of fluorine atoms in the molecule) is preferably suitably changed depending upon the type of the liquid phase to be used for the fluorination reaction. Usually, the fluorine content is preferably at least 10 mass %, particularly preferably from 10 to 86 mass %, especially preferably from 10 to 76 mass %, and further preferably from 30 to 76 mass %. It is preferred to select RA and RB so that the fluorine content will be within such a range.
RA may be a group which contains or does not contain fluorine atoms. Whereas, RB is preferably a perhalogeno group, particularly preferably a perfluoro group, since the after-mentioned continuous process can easily be carried out.
The compound (II) may be a commercial product or the compound (VI) formed by the after-described method of the present invention.
As described above, E2 in the compound (II) is preferably xe2x80x94COX or xe2x80x94SO2X (wherein X is a halogen atom, preferably a chlorine atom or a fluorine atom, and when a continuous process is carried out, X is preferably a fluorine atom), particularly preferably xe2x80x94COX.
Namely, the compound (II) is preferably a compound (IIb) wherein E2 is xe2x80x94COF, particularly preferably a compound (IIb-1) wherein RB is RBF1, especially preferably a compound (IIb-2) wherein RB is R2.
FCORB (IIb) FCORBF1 (IIb-1) FCOR2 (IIb-2)
Here, RB has the same meaning as the meaning in the compound (II). RBF1 is a perhalogeno monovalent saturated hydrocarbon group or a perhalogeno(hetero atom-containing monovalent saturated hydrocarbon) group. R2 is a perhalogenoalkyl group or a perhalogeno(alkoxyalkyl) group.
RBF1 is preferably RBF10 (wherein RBF10 is a perfluoro monovalent saturated hydrocarbon group, a perfluoro(partially chlorinated monovalent saturated hydrocarbon) group, a perfluoro(hetero atom-containing monovalent saturated hydrocarbon) group or a perfluoro(partially chlorinated hetero atom-containing monovalent saturated hydrocarbon) group).
The halogen atom in R2 is preferably a fluorine atom, a chlorine atom or a bromine atom. Further, halogen atoms in R2 may be of one type or two or more types, and particularly preferred is a case where all of the halogen atoms in R2 are fluorine atoms, or 1 or 2 halogen atoms in R2 are chlorine atoms or bromine atoms and all of other halogen atoms are fluorine atoms. R2 is preferably a perfluoroalkyl group, a perfluoro(partially chlorinated alkyl) group, a perfluoro(alkoxyalkyl) group or a perfluoro(partially chlorinated alkoxyalkyl) group.
When R2 is a perhalogenoalkyl group, the carbon number is preferably from 1 to 20, particularly preferably from 1 to 10. Such a group may be of a straight chain structure or a branched structure. When the perhalogenoalkyl group is of a straight chain structure, it may, for example, be xe2x80x94CF3, xe2x80x94CF2CF3, xe2x80x94CF2CF2CF3, xe2x80x94CF2CF2CF2CF3, xe2x80x94CClF2, xe2x80x94CBrF2 or xe2x80x94CF2CFClCF2Cl. When the perhalogeno alkyl group is of a branched structure, it may, for example, be xe2x80x94CF(CF3)2, xe2x80x94CF2CF(CF3)2, xe2x80x94CF(CF3)CF2CF3 or xe2x80x94C(CF3)3.
When R2 is a perhalogeno(alkoxyalkyl) group, the structure of the alkoxyalkyl group moiety is preferably a structure having one hydrogen atom present in a C1-20 (preferably C1-10) alkyl group substituted by a C1-8 alkoxy group.
As an example of a case where R2 is a perhalogeno(alkoxyalkyl) group, xe2x80x94CF(OCF2CF2CF3)CF3, xe2x80x94CF(OCF2CF2CFClCF2Cl)CF3 or xe2x80x94CF(OCF2CF2Br)CF3 may, for example, be mentioned.
From the usefulness of the product, the compound (IIb-2) is preferably the following compound (IIb-3) (wherein each of R8 and R9 which are independent of each other, is a perhalogenoalkyl group), a compound (IIb-2) wherein R2 is xe2x80x94CF2CFClCF2Cl, or CF3CF2COF.
FCOCFR8(OR9) (IIb-3)
The following compounds may be mentioned as specific examples of the compound (II):
CF3CF2COF,
CF2ClCFClCF2COF,
CF2ClCF2CFClCOF,
CF3(CF3CF2CF2O) CFCOF,
CF3(CF2ClCFClCF2CF2O) CFCOF,
CClF2COF,
CBrF2COF,
CF3(CF2BrCF2O)CFCOF,
CF3[CF2ClCFClCF2CF(CF3)O]CFCOF,
CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF,
CF3(CH3CH2CH2O)CFCOF,
CH2ClCHClCH2COCl.
As the compound (II), CF3(CF3CF2CF2O)CFCOF is particularly preferred. This compound can be readily available as an intermediate for a perfluoro(alkyl vinyl ether).
The reaction of the compound (I) with the compound (II) can be carried out by applying known reaction methods and conditions depending upon the structures of E1 and E2 and their combination. For example, the reaction of the compound (Ia) wherein E1 is xe2x80x94CH2OH with a compound (IIb) wherein E2 is xe2x80x94COX, can be carried out under known reaction conditions. Such reaction may be carried out in the presence of a solvent (hereinafter referred to as solvent 1), but it is preferred to carry out the reaction in the absence of solvent 1, from the viewpoint of the volume efficiency. In a case where solvent 1 is used, dichloromethane, chloroform, triethylamine or a solvent mixture of triethylamine with tetrahydrofuran, is preferred. The amount of solvent 1 is preferably from 50 to 500 mass %, based on the total amount of the compound (Ia) and the compound (IIb).
In the reaction of the compound (Ia) with the compound (IIb), an acid represented by HX will be formed. When a compound wherein X is a fluorine atom is used as the compound (IIb), HF will be formed, and as a capturing agent for HF, an alkali metal fluoride (preferably NaF or KF) or a trialkylamine may be present in the reaction system. It is preferred to use a capturing agent for HF, when the compound (Ia) or the compound (IIb) is a compound which is unstable against an acid. Further, when a capturing agent for HF is not used, it is preferred to discharge HF out of the reaction system as accompanied in a nitrogen stream. When an alkali metal fluoride is employed, its amount is preferably from 1 to 10 mol times, based on the compound (IIb).
The temperature for the reaction of the compound (Ia) with the compound (IIb) is usually preferably at least xe2x88x9250xc2x0 C., and preferably at most +100xc2x0 C. or at most the boiling point temperature of the solvent. Further, the reaction time of such a reaction may be suitably changed depending upon the supply rates of the starting materials and the amounts of the compounds to be used for the reaction. The reaction pressure (gauge pressure, the same applies hereinafter) is preferably from atmospheric pressure to 2 MPa.
Explanation About the Compound (III)
By the reaction of the compound (I) with the compound (II), a compound (III) will be formed. In the compound (III), RA is the same group as RA in the compound (I), and RB is the same group as RB in the compound (II). E is a bivalent connecting group formed by the reaction of E1 with E2, and the above-mentioned groups may be mentioned. The molecular weight of the compound (III) is preferably from 200 to 1000, whereby the fluorination reaction in a liquid phase can be smoothly carried out. If the molecular weight is too small, the compound (III) tends to be readily volatile, and it is likely that a decomposition reaction may take place in a gas phase during the fluorination reaction in a liquid phase. On the other hand, if the molecular weight is too large, purification of the compound (III) tends to be difficult.
Further, the fluorine content in the compound (III) is preferably the above-mentioned amount. The compound (III) is preferably a compound (IIIc) which is formed by the reaction of the compound (Ia) with the compound (IIb), particularly preferably a compound (IIIc-1) which is formed by the reaction of the compound (Ia-1) with the compound (IIb-1), especially preferably a compound (IIIc-2) which is formed by the reaction of a compound (Ia-2) with a compound (IIb-2):
RACH2OCORB (IIIc) RAHCH2OCORBF1 (IIIc-1) R1CH2OCOR2 (IIIc-2)
wherein RA, RB, RAH, RBF1, R1 and R2 have the same meanings as described above, and the preferred embodiments are also the same.
The compound (IIIc-2) is preferably a compound (IIIc-20) wherein R1 is R4 (R5O)CHxe2x80x94, a compound (IIIc-21) wherein R2 is xe2x80x94CFR8(OR9), or CF3CF2COOCH2CH2CH3 wherein R1 is an ethyl group, and R2 is a pentafluoroethyl group. Further, the compound (IIIc-2) is preferably a compound (IIIc-3) wherein R1 is R4(R5O)CHxe2x80x94, and R2 is xe2x80x94CFR8(OR9), especially preferably a compound (IIIc-30):
R4(R5O)CHCH2OCOR2 (IIIc-20) R1CH2OCOCFR8(OR9) (IIIc-21) R4(R5O)CHCH2OCOCFR8(OR9) (IIIc-3) CH3(CH3CH2CH2O)CHCH2OCOCFR8(OR9) (IIIc -30)
The following compounds may be mentioned as specific examples of the compound (III):
CF3CF2COOCH2CH2CH3,
CF3CF2COOCH2CH(OCH2CH2CH3)CH3,
CF3CF2COOCH2CH(OCH2CH2CHClCH2Cl)CH3,
CF3CF2COO(CH2)4OCHClCH2Cl,
CF3CF2COO(CH2)5OCHClCH2Cl,
CF3(CF3CF2CF2O)CFCOO(CH2)4OCHClCH2Cl,
CF3(CF3CF2CF2O)CFCOO(CH2)5OCHClCH2Cl,
CF3(CF2ClCFClCF2CF2O)CFCOOCH2CH(OCH2CH2CHClCH2Cl)CH3,
CF2ClCFClOCF2CF2CF2COO(CH2)4OCHClCH2Cl,
CClF2COOCH2CH2Cl,
CBrF2COOCH2CH2Br,
CF2BrCF2OCF(CF3COOCH2CH(OCH2CH2Br) CH3,
CF2ClCFClCF2CF(CF3)OCF(CF3)COOCH2CH[OCH(CH3)CHClCH2Cl]CH3,
CH2ClCHClCH2COOCH2CF2CFClCF2Cl,
CF3(CH3CH2CH2O)CFCOOCH2CF(OCF2CF2CF3)CF3,
CF3(CH3CH2CH2O)CFCOOCH2CF(OCH2CH2CH3)CF3,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2CH2CH3)CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2CH2CHClCH2Cl)CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2Cy)CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(OCH2Ph)CH3,
CF3(CF3CF2CF2O)CFCOOCH2CH(O(CH2)9CH3)CH3,
CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2Ph,
CF3(CF3CF2CF2O)CFCOO(CH2)3OCH2CHxe2x95x90CH2,
CF3CF2COOCH2CH2CHClCH2Cl,
CF2ClCFClCF2COOCH2CH2CHClCH2Cl,
CF2ClCF2CFClCOOCH2CH2CHClCH2Cl, 
The above-mentioned novel compound (III) is useful as an intermediate for a fluorinated resin material, and can be led to a fluorinated resin material by the after-described reaction. Especially in the novel compound (III), a compound having xe2x80x94CHClCH2Cl at its molecular terminals can be led to a fluorinated resin material having two polymerizable unsaturated groups.
A crude product containing the compound (III) formed by the reaction of the compound (I) with the compound (II), may be purified depending upon the particular purpose or may be used for the next reaction as it is. With a view to carrying out the fluorination reaction of the next step safely, it is preferred that the compound (III) in the crude product is separated and purified.
The purification method of the crude product may, for example, be a method of distilling the crude product directly, a method of treating the crude product with a dilute alkali water, followed by liquid separation, a method of extracting the crude product with a suitable organic solvent, followed by distillation, or silica gel column chromatography.
Explanation About the Compound (IVd)
Then, in the present invention, the compound (III) is fluorinated in a liquid phase to obtain a compound (IV). The fluorination in a liquid phase is preferably carried out by a method of fluorinating the compound (IIIc) in a solvent with fluorine gas (fluorination method-1) or by electrochemical fluorination (fluorination method-2), particularly preferably fluorination method-1.
When fluorination is carried out by fluorination method-2, it is preferred that the compound (III) is dissolved in anhydrous hydrofluoric acid to obtain a solution, and this solution is electrolyzed in an electrolytic cell to fluorinate the compound (III) to form a compound (IV).
When fluorination is carried out in fluorination method-1, the compound (III) and fluorine gas are reacted in a solvent (hereinafter referred to as solvent-2) to form a compound (IV). The fluorine gas may be used as it is, or fluorine gas diluted with an inert gas may be employed. As the inert gas, nitrogen gas or helium gas is preferred, and nitrogen gas is particularly preferred from an economical reason. The amount of fluorine gas in the nitrogen gas is not particularly limited, and at least 10% is preferred from the viewpoint of the efficiency, and at least 20% is particularly preferred.
Solvent-2 to be used for fluorination method-1 is preferably a solvent which contains no Cxe2x80x94H bond and which necessarily contains a Cxe2x80x94F bond. Further, a perfluoroalkane or an organic solvent obtained by perfluorinating a known organic solvent having at least one atom selected from a chlorine atom, a nitrogen atom and an oxygen atom in its structure, is preferred. Further, as solvent-2, it is preferred to employ a solvent which provides a high solubility to the compound (III), and it is particularly preferred to employ a solvent which is capable of dissolving at least 1 mass % of the compound (III), particularly a solvent which is capable of dissolving at least 5 mass %.
Examples of solvent-2 may be a compound (IIb-2), an after-described compound (IVd-2), perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75 and FC-77), perfluoropolyethers (tradenames: KRYTOX, FOMBLIN, GALDEN and Demnum), chlorofluorocarbons (tradename: Flon Lube), chlorofluoropolyesters, perfluoroalkylamines [such as perfluorotrialkylamine], and an inert fluid (tradename: Fluorinert). Among them, a perfluorotrialkylamine, the compound (V) or the compound (VI) (preferably the compound (IIb-2), the compound (IV) (preferably the compound (IVd-2)) is preferred. Particularly when the compound (IV), the compound (V) or the compound (VI) is employed, there will be a merit that workup after the reaction will be easy. The amount of solvent-2 is preferably at least five times by mass, particularly from 10 to 100 times by mass, relative to the compound (III).
The reaction type of the fluorination reaction of fluorination method-1 is preferably a batch system or a continuous system. Especially from the viewpoint of the reaction yield and selectivity, a continuous system (2) which will be described hereinafter, is preferred. Further, fluorine gas may be one diluted with an inert gas such as nitrogen gas either when the reaction is carried out by a batch system or when it is carried out by a continuous system.
Continuous system (1) Into a reactor, the compound (III) and solvent-2 are charged, and stirring is initiated. A method of reacting at a predetermined reaction temperature and reaction pressure while supplying fluorine gas continuously.
Continuous system (2) Into a reactor, solvent-2 is charged, and stirring is initiated. A method of supplying the compound (III), solvent-2 and fluorine gas under a predetermined reaction temperature and reaction pressure in a predetermined molar ratio continuously and simultaneously. In the continuous system (2), when the compound (III) is supplied, it is preferred to supply the compound (III) as diluted with solvent-2, to improve the selectivity and to suppress the amount of by-products. Further, in the continuous system (2), when the compound (III) is diluted with the solvent, it is preferred to adjust the amount of solvent-2 to at least five times by mass, particularly preferably at least ten times by mass, relative to the compound (III).
With respect to the amount of fluorine to be used for the fluorination reaction, when the reaction is carried out by a batch system, it is preferred to charge fluorine gas so that the amount of fluorine atoms is always excess equivalent, relative to hydrogen atoms in the compound (III), and it is particularly preferred that fluorine gas is used so that it becomes at least 1.5 times by equivalent, from the viewpoint of selectivity. Further, when the reaction is carried out by a continuous process, it is preferred to continuously supply fluorine gas so that the amount of fluorine atoms will be excess equivalent, relative to hydrogen atoms in the compound (III), and it is particularly preferred to continuously supply fluorine gas so that it becomes at least 1.5 times by equivalent, relative to the compound (III), from the viewpoint of selectivity.
The reaction temperature for the fluorination reaction by fluorination method-1 may be varied depending upon the structure of the bivalent connecting group (E), but it is usually preferably at least xe2x88x9260xc2x0 C. and at most the boiling point of the compound (III), and from the viewpoint of the reaction yield, the selectivity and efficiency for industrial operation, it is particularly preferably from xe2x88x9250xc2x0 C. to +100xc2x0 C., especially preferably from xe2x88x9220xc2x0 C. to +50xc2x0 C. The reaction pressure of the fluorination reaction is not particularly limited, and it is particularly preferably from atmospheric pressure to 2 MPa from the viewpoint of the reaction yield, the selectivity and efficiency for industrial operation.
Further, in order to let fluorination method-1 proceed efficiently, it is preferred to add a Cxe2x80x94H bond-containing compound to the reaction system or to carry out in the presence of ultraviolet light. For example, in a batch system reaction, it is preferred to add a Cxe2x80x94H bond-containing compound to the reaction system or to carry out in the presence of ultraviolet light at a later stage of the fluorination reaction. In a continuous system reaction, it is preferred to add a Cxe2x80x94H bond-containing compound, or to carry out in the presence of ultraviolet light, whereby the compound (III) present in the reaction system can efficiently be fluorinated, and the reaction rate can remarkably be improved. The time for ultraviolet irradiation is preferably from 0.1 to 3 hours.
The Cxe2x80x94H bond-containing compound is an organic compound other than the compound (III), and an aromatic hydrocarbon is particularly preferred. Especially preferred is, for example, benzene or toluene. The amount of such a Cxe2x80x94H bond-containing compound is preferably from 0.1 to 10 mol %, particularly preferably from 0.1 to 5 mol %, relative to hydrogen atoms in the compound (III).
It is preferred to add the Cxe2x80x94H bond-containing compound in such a state where fluorine gas is present in the reaction system. Further, when the Cxe2x80x94H bond-containing compound is added, it is preferred to pressurize the reaction system. The pressure during the pressurizing is preferably from 0.01 to 5 MPa.
In the fluorination reaction of the compound (III), a compound (IV) will be formed. In the compound (IV), RAF is a group corresponding to RA, and RBF is a group corresponding to RB. In a case where each of RA and RB is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group or a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group, each of RAF and RBF is the same group as RA and RB, respectively, or a group having at least one hydrogen atom present in the group of RA or RB substituted by a fluorine atom. RAF and RBF are preferably groups which are substituted by fluorine, and in such groups, non-substituted hydrogen atoms may be present. The amounts of hydrogen atoms in such groups are preferably suitably changed depending upon the particular purpose.
Further, when a compound (III) wherein hydrogen atoms are present in RA and RB, is fluorinated, RAF and RBF in the compound (IV) to be formed, may be groups wherein He hydrogen atoms may or may not be present, preferably groups wherein no hydrogen atoms are present, particularly preferably groups wherein all of hydrogen atoms in RA and RB are substituted by fluorine atoms.
Further, in a case where even if hydrogen atoms are present in RA and RB, such hydrogen atoms are not susceptible to fluorination, or in a case where a compound (III) wherein RA and RB are perhalogeno groups, is employed, RAF and RBF in the compound (IV) are the same groups as RA and RB, respectively. In a case where RA and RB are monovalent organic groups (RH), RAF and RBF are RHF corresponding to such RH, respectively.
In the fluorination reaction in a liquid phase, it is difficult to adjust the position for introduction of a fluorine atom, and accordingly, RAF and RBF in the compound (IV) are preferably groups which contain no hydrogen atoms. Namely, when a compound (III) wherein each of RA and RB is a group containing hydrogen atoms, is employed, it is preferred to obtain a compound (IV) having RAF and RBF wherein all of such hydrogen atoms are substituted by fluorine atoms.
Each of RAF and RBF is preferably a perfluoro monovalent saturated hydrocarbon group, a perfluoro(partially halogeno monovalent saturated hydrocarbon) group, a perfluoro(hetero atom-containing monovalent saturated hydrocarbon) group, or a perfluoro[partially halogeno(hetero atom-containing monovalent saturated hydrocarbon)] group.
EF is the same group as E, or a group having E fluorinated. An example of the latter group may be a group having at least one hydrogen atom present in E fluorinated, or in a case where a xe2x80x94CHxe2x95x90CHxe2x80x94 moiety is present in E, a group having fluorine atoms added to such moiety to form xe2x80x94CF2CF2xe2x80x94. Further, the compound (IV) is not of the same structure as the compound (III), and at least one of RAF, RBF and EF is of a structure different from the corresponding RA, RB and E, respectively. Namely, at least one of RA, RB and E is a group modified by the fluorination reaction.
The compound (IV) is preferably a compound (IVd) which is formed by fluorination of a compound (III) wherein E is xe2x80x94CH2OCOxe2x80x94, particularly preferably a compound (IVd-1) which is formed by completely fluorinating the compound (IIIc-1), especially preferably a compound (IVd-2) which is formed by completely fluorinating the compound (IIIc-2):
RAFCF2OCORBF (IVd) RAF1CF2OCORBF1 (IVd-1) R3CF2OCOR2 (IVd-2)
wherein RAF and RBF: the same meanings as the meanings in the compound (IV);
RAF1: RAF1 is a group corresponding to RAH, and when RAH is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms, and when RAH is a group containing no hydrogen atom, the same group as RAH;
RBF1: A perhalogeno monovalent saturated hydrocarbon group or a perhalogeno(hetero-atom-containing monovalent saturated hydrocarbon) group;
R3: A group corresponding to R1, and when R1 is a group containing no hydrogen atom, the same group as R1, and when R1 is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms;
R2: The same group as R2 in (IIIc-2).
Further, from the viewpoint of usefulness, the compound (IVd-2) is preferably a compound (IVd-20) where R3 is R6(R7O)CFxe2x80x94, a compound (IVd-21) where R2 is xe2x80x94CFR8(OR9), or perfluoro(propyl propionate) where R2 and R3 are perfluoroethyl groups:
R6(R7O)CFCF2 OCOR2(IVd-20) R3CF2OCOCFR8(OR9) (IVd-21)
wherein R2, R3: The same meanings as described above;
R6: A group corresponding to R4, and when R4 is a group containing no hydrogen atom, the same group as R41 and when R4 is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms;
F7: A group corresponding to R5, and when R5 is a group containing no hydrogen atom, the same group as R5, and when R7 is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms;
R8, R9: The same meanings as described above.
Further, the compound (IVd-2) is preferably a compound (IVd-3) where R3 is R6(R7O)CFxe2x80x94, and R2 is xe2x80x94CFR8(OR9). Such compound (IVd-3) can be produced by the following production route. Namely, it is obtainable by reacting the compound (Ia-3) with the compound (IIb-3) to form a compound (IIIc-3) and fluorinating the compound (IIIc-3) in a liquid phase (preferably by reacting with fluorine gas in a solvent). The symbols in the following formulae have the same meanings as described above.
R4(R5O)CHCH2OH(Ia-3)+FCOCFR8(OR9) (IIb-3)xe2x86x92R4(R5O)CHCH2OCOCFR8(OR9) (IIIc-3)xe2x86x92R6 (R7O) CFCF2OCOCFR8(OR9) (IVd-3)
The following compounds may be mentioned as specific examples of the compound (IV):
CF3CF2COOCF2CF(OCF2CF2CF3)CF3,
CF3CF2COOCF2CF(OCF2CF2CFClCF2Cl)CF3,
CF3(CF2ClCFClCF2CF2O)CFCOOCF2CF(OCF2CF2CFClCF2Cl)CF3,
CClF2COOCF2CF2Cl,
CBrF2COOCF2CF2Br,
CF3(CF2BrCF2O)CFCOOCF2CF(OCF2CF2Br)CF3,
CF3[CF2ClCFClCF2CF(CF3)O]CFCOOCF2CF[OCF(CF3)CF2CFClCF2Cl ]CF3,
CF3CF2COOCF2CF(OCHFCF2CFClCF2Cl)CF3,
CF3(CF3CF2CF2O)CFCOOCF2CF(OCHFCF2CFClCF2Cl)CF3,
CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CF3)CF3,
CF3CF2COOCF2CF2CF3,
CF3CF2COOCF2CF2CFClCF2Cl,
CF2ClCFClCF2COOCF2CF2CFClCF2Cl,
CF2ClCF2CFClCOOCF2CF2CFClCF2Cl,
CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CFClCF2Cl)CF3.
CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CYF)CF3,
CF3(CF3CF2CF2O)CFCOOCF2CF(O(CF2)9CF3)CF3,
CF3(CF3CF2CF2O)CFCOO(CF2)3OCF2CYF,
CF3(CF3CF2CF2O)CFCOO(CF2)3OCF2CF2CF3, 
In the liquid-phase fluorination reaction of the compound (III), when a reaction to substitute hydrogen toms with fluorine atoms takes place, HF will be formed as a by-product. To remove HF formed as a by-product, it is preferred to incorporate an HF scavenger in the reaction system or to contact the outlet gas with an HF scavenger at the gas outlet of the reactor. As such an HF scavenger, the same as described above may be employed, and NaF is preferred.
When the HF scavenger is incorporated in the reaction system, the amount is preferably from 1 to 20 mol times, more preferably from 1 to 5 mol times, relative to the total amount of hydrogen atoms present in the compound (III). In a case where the HF scavenger is disposed at the outlet of the reactor, it is preferred to arrange (1) a condenser (preferably maintained at a temperature of from 10xc2x0 C. to room temperature, particularly preferably at about 20xc2x0 C.) (2) a NaF pellet packed layer and (3) a condenser (preferably maintained at a temperature of from xe2x88x9278xc2x0 C. to +10xc2x0 C., more preferably from xe2x88x9230xc2x0 C. to 0xc2x0 C.) in a series in the order of (1)-(2)-(3). Further, a liquid-returning line may be installed to return the condensed liquid from the condenser of (3) to the reactor.
The crude product containing the compound (IV) obtained by the fluorination reaction may be employed for the next step as it is or may be purified to a high purity. The purification method may, for example, be a method of distilling the crude product as it is under atmospheric pressure or reduced pressure.
Explanation About the Compound (Ve)
In the present invention, the compound (IV) is further converted to a compound (V). Such a conversion reaction is a reaction to dissociate EF in the compound (IV) into EF1 and EF2. The method and conditions of the conversion reaction may suitably be changed depending upon the structure of the compound (IV). In a case where the compound (IV) is a compound (IVd), the conversion reaction is a reaction to dissociate xe2x80x94CF2OCOxe2x80x94.
The conversion reaction of the compound (IVd) is preferably carried out by a thermal decomposition reaction or a decomposition reaction which is carried out in the presence of a nucleophile or an electrophile. By such a reaction, a compound (Ve) and the compound (VIf) wherein EF1 and EF2 are xe2x80x94COF, will be formed.
The thermal decomposition reaction can be carried out by heating the compound (IVd). The reaction type of the thermal decomposition reaction is preferably selected from the boiling point and the stability of the compound (IVd). For example, when a compound (IVd) which is readily vaporized, is to be thermally decomposed, a gas phase thermal decomposition method may be employed in which it is continuously decomposed in a gas phase, and the outlet gas containing the obtained compound (Ve) is condensed and recovered.
The reaction temperature of the gas phase thermal decomposition method is preferably from 50 to 350xc2x0 C., particularly preferably from 50 to 300xc2x0 C., especially preferably from 150 to 250xc2x0 C. Further, an inert gas which is not concerned directly with the reaction, may be present in the reaction system. As such an inert gas, nitrogen or carbon dioxide may, for example, be mentioned. It is preferred to add an inert gas in an amount of from 0.01 to 50 vol % relative to the compound (IVd). If the amount of the inert gas is large, the recovery of the product may sometimes decrease. The method and conditions of the gas phase decomposition method can be applied to any compound contained in the scope of the compound (IVd).
On the other hand, in a case where the compound (IV) is a compound which is hardly vaporized, it is preferred to employ a liquid phase thermal decomposition method wherein it is heated in the state of a liquid in the reactor. The reaction pressure in this case is not limited. In a usual case, the product containing the compound (Ve) is of a lower boiling point, and it is preferred to obtain the product by a method of a reaction distillation type wherein the product is vaporized and continuously withdrawn. Otherwise, it may be a method wherein after completion of the heating, the product is withdrawn all together from the reactor. The reaction temperature for this liquid phase thermal decomposition method is preferably from 50 to 300xc2x0 C., particularly preferably from 100 to 250xc2x0 C.
When the thermal decomposition is carried out by the liquid phase thermal decomposition method, the decomposition may be carried out in the absence of a solvent or in the presence of a solvent (hereinafter referred to as solvent-3). Solvent-3 is not particularly limited so long as it is not reactive with the compound (IVd) and it is compatible with the compound (IVd) and is not reactive with the resulting compound (Ve). Further, as solvent-3, it is preferred to select one which is readily separable at the time of purification of the compound (Ve). A specific example of solvent-3 may be an inert solvent such as perfluorotrialkylamine or perfluoronaphthalene, or a chlorofluorocarbon, particularly preferably chlorotrifluoroethylene oligomer having a high boiling point (for example, tradename: Flon Lube). Further, the amount of solvent-3 is preferably from 10 to 1000 mass % relative to the compound (IVd).
Further, in a case where the compound (IVd) is decomposed by reacting it with a nucleophile or an electrophile in a liquid phase, such a reaction may be carried out in the absence of a solvent or in the presence of a solvent (hereinafter referred to as solvent-4). Solvent-4 is preferably the same as solvent-3. The nucleophile is preferably a fluoride anion (Fxe2x88x92), particularly preferably a fluoride anion derived from an alkali metal fluoride. The alkali metal fluoride is preferably NaF, NaHF2, KF or CsF. Among them, NaF is particularly preferred from the viewpoint of economical efficiency.
When the nucleophile such as (Fxe2x88x92) is employed, Fxe2x88x92 is nucleophilically added to a carbonyl group present in the ester bond of the compound (IVd), whereby RAFCF2Oxe2x88x92 will be detached, and an acid fluoride [compound (VIf)] will be formed. From RAFCF2Oxe2x88x92, Fxe2x88x92 will further be detached to form an acid fluoride [compound (Ve)]. The detached Fxe2x88x92 will react with another molecule of the compound (VId) in the same manner. Accordingly, the nucleophile to be used at the initial stage of the reaction may be in a catalytic amount or may be used excessively. Namely, the amount of the nucleophile such as Fxe2x88x92 is preferably from 1 to 500 mol %, particularly preferably from 10 to 100 mol %, especially preferably from 5 to 50 mol %, relative to the compound (IVd). The reaction temperature is preferably from xe2x88x9230xc2x0 C. to the boiling point of the solvent or the compound (IVd), particularly preferably from xe2x88x9220xc2x0 C. to 250xc2x0 C. This method is also preferably carried out by the distillation column type production method.
In the conversion reaction of the compound (IVd), the compound (Ve) and/or the compound (VIf) will be formed; in the conversion reaction of the compound (IVd-1), the compound (Ve-1) and/or the compound (VIf-1) will be formed; in the thermal decomposition of the compound (IVd-2), the compound (Ve-2) and/or the compound (IIb-2) will be formed; and in the thermal decomposition of the compound (IVd-3), the compound (Ve-3) and/or the compound (VIe-3) will be formed.
RAFCOF (Ve) RBFCOF (VIf) RAF1COF (Ve-1) RBF1COF (VIf-1) R3COF (Ve-2) R2COF (IIb-2) R6(R7O)CFCOF (Ve-3) R8(R9O)CFCOF (VIe-3)
wherein the meanings of AF, BF, R2, R3, R6 to R9 and RBF1 are the same as the above meanings, and RAF1 is a group corresponding to RAH, and each represents a perhalogeno monovalent saturated hydrocarbon group or a perhalogeno(hetero atom-containing monovalent saturated hydrocarbon) group.
The following compounds may be mentioned as specific examples of the compound (Ve):
xe2x80x83CF3CF2COF, CF2ClCFClCF2COF, CF2ClCF2CFClCOF, CF3(CF3CF2CF2O)CFCOF, CF3(CF2ClCFClCF2CF2O)CFCOF, CF3(CF2ClCFClCF2CHFO)CFCOF. FCOCF(O(CF2)9CF3)CF3, FCO(CF2)2OCF2CyF,
Among the compound (Ve) and/or the compound (VIf) thereby obtainable, a compound having a partial structure of xe2x80x9cC1Fxe2x80x94C2xe2x80x94COFxe2x80x9d at the molecular terminals, can be led to a fluorine resin material by converting the molecular terminals to xe2x80x9cC1xe2x95x90C2xe2x80x9d by a known reaction (Methods of Organic Chemistry, 4, Vol.10b, Part 1, p.703, etc.). Namely, the novel compound (Ve) and/or the compound (VIf) is a compound useful as a precursor for a fluorinated resin material. Further, the novel compound (IIIc) and compound (IVd) are compounds useful as intermediates for such precursors.
The novel compound presented by the present invention, can be led to a useful fluorinated resin material by a method which will be described below. Namely, a compound (IIb) or a compound (IIIc) wherein RB and RBF are CF3(CF3CF2CF2O)CFxe2x80x94, can be led to a compound (IIb-30) which is a precursor for a useful fluorinated resin material (CF3CF2CF2OCFxe2x95x90CF2) by the following route. For example, the production route wherein RB and RBF are CF3(CF3CF2CF2O)CFxe2x80x94, will be represented as follows:
RACH2OH+FOCOCF(OCF2CF2CF3)CF3xe2x86x92RACH2OCOCF(OCF2CF2CF3)CF3xe2x86x92RAFCF2OCOCF(OCF2CF2CF3)CF3xe2x86x92RAFCOF+CF3(CF3CF2CF2O)CFCOF(IIb-30)xe2x86x92CF3CF2CF2OCFxe2x95x90CF2
Further, in a case where an unsaturated bond is present in RA in the compound (IIb) (for example, a phenyl is present in RA), a product (IIb-30) will be obtained by the following reaction:
CH3(PhCH2O)CHCH2OH+FCOCF(OCF2CF2
CF3)CF3xe2x86x92CH3(PhCH2O)CHCH2
OCOCF(OCF2CF2CF3)CF3
xe2x86x92CF3(CYFCF2O)CFCF2
OCOCF(OCF2CF2CF3)CF3
xe2x86x92CF3(CYFCF2O)CFCOF+FCOCF(OCF2
CF2CF3)CF3(IIb-30)
Further, in a case where RA in the compound (IIb-1) is CH2ClCHClxe2x80x94, such a compound can be led to a compound (IIb-21) useful as a perfluoro(butenyl vinyl ether) [CF2xe2x95x90CFCF2CF2OCFxe2x95x90CF2] material by the following production route:
CH2ClCHClCH2CH2OCORBxe2x86x92CF2
ClCFClCF2CF2OCORBxe2x86x92CF2ClCFClCF2
COF(IIb-21)+FCORB
Further, CF3CF2COOCF2CF2CF3 can be led to CF3CF2COF (IIb-20) useful as a pentafluoropropionyl fluoride material by the method of the present invention. The compound (IIb-20) may be added to the reaction system for the dimerization reaction of hexafluoropropylene oxide, whereby compound (IIb-30) can be produced efficiently (JP-A-11-116529, etc).
Further, in a case where the compound (IIb) is a compound wherein RA is a dioxolane skeleton, it produces a compound (IIb-30) and it can be led to a known fluorinated resin material by the following production route: 
Explanation About Various Production Processes
In the conversion reaction of the compound (IV), the compound (VI) will be formed together with the compound (V). The desired compound in the process for producing of the present invention may be the compound (V) only, the compound (VI) only, or both the compound (V) and the compound (VI).
Further, the process of the present invention can be made to be the following efficient processes 1 to 3 by selecting groups in compounds. In the following, the groups not defined have the same meanings as described above.
Process 1
A process wherein groups are selected so that the compound (V) and the compound (VI) will be the same compound. By this process, the step of separating the product can be omitted.
For example, there may be mentioned a case where groups are selected so that RAF and RBF in the compound (IVd) will be of the same structure, and likewise a case where groups are selected so that RAF1 and RBF1 in the compound (IVd-1) will be of the same structure. Specific examples of such Process 1 will be exemplified in Process 3.
Process 2
A process wherein a group in the compound (II) is selected so that the resulting compound (VI) will be of the same structure as the compound (II). According to such a process, the resulting compound (VI) (=the compound (II)) can be used again for the reaction with the compound (I), whereby the process of the present invention can be made to be a continuous production process.
A specific example of Process 2 may be an example wherein a perhalogeno group is used as RBF in the compound (IIb). For example, when a compound (IIb-10) is used as the compound (IIb), the process can be made to be the following production process.
Namely, it is a continuous process for producing a compound (Ve) wherein the compound (Ia) and the compound (IIb-10) are reacted to form a compound (IIIc-10); the compound (IIIc-10) is fluorinated in a liquid phase to form a compound (IVd-10); then the compound (IVd-10) is converted (preferably subjected to a thermal decomposition reaction) to obtain a compound (Ve) and a compound (IIb-10), and a part or whole of the compound (IIb-10) is used again for the reaction with the compound (Ia):
RACH2OH (Ia)+FCORBF10 (IIb-10)xe2x86x92
RACH2OCORBF10 (IIIc-10)xe2x86x92
RAFCF2OCORBF10 (IVd-10)xe2x86x92
RAFCOF (Ve)+compound (IIb-10)
Likewise, it is a continuous process for producing a compound (Ve-1), which comprises a first step of reacting a compound (Ia-1) and a compound (IIb-1) to form a compound (IIIc-1), then reacting the compound (IIIc-1) with fluorine gas in a solvent to form a compound (IVd-1) and then converting (preferably thermally decomposing) the compound (IVd-1) to obtain a compound (IIb-1) together with a compound (Ve-1), a second step of carrying out the same reactions as in the first step by using the compound (IIb-1) obtained by the thermal decomposition in the first step, to obtain a compound (IIb-1) together with the compound (Ve-1), and a further step of repeating the second step by using the compound (IIb-1) obtained by the thermal decomposition in the second step:
RAHCH2OH (Ia-1)+FCORBF1 (IIb-1)xe2x86x92
RAHCH2OCORBF1 (IIIc-1)xe2x86x92
RAF1CF2OCORBF1 (IVd-1)xe2x86x92
RAF1COF (Ve-1)+compound (IIb-1)
Specifically, it is a continuous process wherein a compound (Ia-2) and a compound (IIb-2) are reacted to form a compound (IIIc-2); the compound (IIIc-2) is fluorinated in a liquid phase to form a compound (IVd-2); the compound (IVd-2) is converted (preferably subjected to a thermal decomposition reaction) to obtain a compound (IIb-2) together with a compound (Ve-2); and then a part or whole of the compound (IIb-2) is used again for the reaction with the compound (Ia-2):
R1CH2OH (Ia-2)+FCOR2 (IIb-2)xe2x86x92
R1CH2OCOR2 (IIIc-2)xe2x86x92R3
CF2OCOR2 (IVd-2)xe2x86x92
R3COF (Ve-2)+compound (IIb-2)
Likewise, it is a continuous process wherein in the following production route employing a compound (Ia-30) and a compound (IIb-30), the formed compound (IIb-30) is used again for the reaction with the compound (Ia-30):
(CH3)(CH2ClCHClCH2CH2O)CHCH2
OH (Ia-30)+
FCOCF(CF3)(OCF2CF2CF3) 
(IIb-30)xe2x86x92(CH3)(CH2ClCHClCH2
CH2O)CHCH2OCOCF(CF3)(OCF2CF2
CF3) (IIIc-30)xe2x86x92(CF3)(CF2
ClCFClCF2CF2O)CFCF2OCOCF(CF3)(OCF2
CF2CF3) (IVd-30)xe2x86x92(CF3)(CF2
ClCFClCF2CF2O)CFCOF (IIb-32)+compound (IIb-30)
The compound (IIb-32) can be led to a material for a fluorine resin [CF2xe2x95x90CFCF2CF2OCFxe2x95x90CF2] by a known method.
Further, in the same manner, it can be made to be a continuous process by using the formed compound (IIb-20) again for the reaction with the compound (Ia-20) in the following production route employing the compound (Ia-20) and the compound (IIb-20):
CH2ClCHClCH2CH2OH (Ia-20)+FCOCF2
CF3 (IIb-20)xe2x86x92CH2ClCHClCH2CH2
OCOCF2CF3 (IIIc-40)xe2x86x92CF2ClCFClCF2
CF2OCOCF2CF3 (IVd-40)xe2x86x92FCOCF2
CFClCF2Cl (IIb-21)+compound (IIb-20)
Process 3
A process wherein groups are selected so that the resulting compound (V) and the compound (VI) will be of the same structure and further, they will be of the same structure as compound (II). Such a process is particularly preferred since it is unnecessary to separate the product, and a part or whole of the formed compound can be used again for the reaction with the compound (I).
For example, it is a process for producing a compound (Ve-2) wherein a compound (Ia-2) and a compound (Ve-2) are reacted to form a compound (IIIc-4); the compound (IIIc-4) is fluorinated in a liquid phase to form a compound (IVd-4); and then the compound (IVd-4) is converted (preferably thermally decomposed) to obtain a compound (Ve-2). And, it is a continuous process for producing the compound (Ve-2), wherein a part or whole of the formed compound (Ve-2) is used again for the reaction with the compound (Ia-2):
R1CH2OH (Ia-2)+FCOR3 (Ve-2)xe2x86x92R1
CH2OCOR3 (IIIc-4)xe2x86x92
R3CF2OCOR3 (IVd-4)xe2x86x92FCOR3 
(Ve-2)
Likewise, it is a continuous process for producing a compound (IIb-31), wherein a compound (Ia-3) and a compound (IIb-31) are reacted to form a compound (IIIc-31); the compound (IIIc-31) is reacted with fluorine gas in a solvent to form a compound (IVd-41); and the compound (IVd-41) is converted (preferably thermally decomposed). And, it is a continuous method for producing the compound (IIb-31), wherein a part or whole of the formed compound (IIb-31) is used again for the reaction with the compound (Ia-3):
R4(R5O)CHCH2OH (Ia-3)+
FCOCFR80(OR90) (IIb-31)xe2x86x92R4(R5O)CHCH2OCOCFR80
(OR90) (IIIc-31)xe2x86x92
R80(R90O)CFCF2OCOCFR80
(OR90) (IVd-41)xe2x86x92
compound (IIb-31)
wherein
R80: A group corresponding to R4; and when R4 is a group containing no hydrogen atom, the same group as R4, and when R4 is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms;
R90: A group corresponding to R5; and when R5 is a group containing no hydrogen atom, the same group as R5, and when R5 is a group containing hydrogen atoms, a group having all of hydrogen atoms in such a group substituted by fluorine atoms.
Specifically, there is a continuous process for producing a compound (IIb-30) represented by the following production route employing a compound (Ia-31) and a compound (IIb-30):
(CH3)(CH3CH2CH2O)CHCH2
OH (Ia-31)+FCOCF(CF3)(OCF2
CF2CF3) (IIb-30)xe2x86x92(CH3)(CH3
CH2CH2O)CHCH2OCOCF( CF3)(OCF2
CF2CF3) (IIIc-310)xe2x86x92(CF3)(CF3
CF2CF2O)CFCF2OCOCF(CF3)(OCF2
CF2CF3) (IVd-410)xe2x86x92FCOCF(CF3)(OCF2
CF2CF3) (IIb-30)
In the above process, the compound (IIIc-310) and the compound (IVd-410) are novel compounds. From the compounds, the compound (IIb-30)) can be obtained. The compound (IIb-30) can be led to perfluoro(propylvinyl ether) which is a fluorinated resin material, by a known method. Further, there is a continuous process for producing a compound (IIb-20) represented by the following production route when a compound (Ia-21) and a compound (IIb-20) are employed:
CH3CH2CH2OH 
(Ia-21)+FCOCF2CF3 (IIb-20)xe2x86x92
CH3CH2CH2OCOCF2CF3 (IIIc-41)xe2x86x92
CF3CF2CF2OCOCF2CF3 (IVd-41)xe2x86x92
compound (IIb-20)
Likewise, specifically, there is a continuous process for producing a compound (IIb-21) represented by the following production route employing a compound (Ia-20) and a compound (IIb-21):
CH2ClCHClCH2CH2OH (Ia-20)+FCOCF2
CFClCF2Cl (IIb-21)xe2x86x92
CH2ClCHClCH2CH2OCOCF2
CFClCF2Cl (IIIc-42)xe2x86x92
CF2ClCFClCF2CF2OCOCF2
CFClCF2Cl (IVd-42)xe2x86x92
compound (IIb-21)
According to the process of the present invention, it is possible to produce various fluorine-containing compounds by using the compound (I) and the compound (II) which are inexpensively available materials. With respect to the compound (I) and the compound (II), various compounds which are different in the structure of RA or the structure of RB, are commercialized and inexpensively available. And, according to the process of the present invention, from such starting material compounds, a fluorine-containing compound such as an acid fluoride compound can be produced by a short process in good yield. Further, by using the process of the present invention, a low molecular fluorine-containing compound which used to be difficult to obtain by a conventional process, or a fluorine-containing compound having a complex structure, can easily be synthesized. Further, the process of the present invention is a process excellent in wide applicability, which can be applied to various compounds without being limited to the compounds described above as specific examples. Accordingly, a fluorine-containing compound having a desired skeleton can freely be produced. Further, by selecting the structures of RA and RB, the process of the present invention can be made to be a continuous process.
Further, according to the present invention, a novel acid fluoride compound or its intermediate can be provided which can be used as a fluorinated resin material.
In the foregoing description, the reaction conditions (such as the amounts of the respective compounds to be reacted, the temperatures, the pressures, etc.), etc. in the process of the present invention were specifically described with respect to the compound (Ia), the compound (IIb), the compound (IIIc), the compound (IVd) and the compound (Ve). However, the above-described reaction conditions can be applicable also in cases wherein various compounds included in such compounds, and the compounds (I) to (IV) are employed. Specifically, for example, in the case of the compound (Ia), a compound (Ia-1), a compound (Ia-2) or a compound (Ia-3) may, for example, be mentioned; in the case of the compound (IIb), a compound (IIb-1), a compound (IIb-2) or a compound (IIb-3) may, for example, be mentioned; in the case of the compound (IIIc), a compound (IIIc-1), a compound (IIIc-2) or a compound (IIIc-3) may, for example, be mentioned; in the case of a compound (IVd), a compound (IVd-1), a compound (IVd-2) or a compound (IVd-3) may, for example, be mentioned; and in the case of the compound (Ve), a compound (Ve-1), a compound (Ve-2) or a compound (Ve-3) may, for example, be mentioned.